SPE 160840

Aqueous Foams Stabilized with Particles and Surfactants

Zhaomin Li, Zupeng Liu, Binfei Li, Songyan Li,Qian Sun, Shuhua Wang, College of Petroleum Engineering, China
University of Petroleum (East China)

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Saudi Arabia Section Technical Symposium and Exhibition held in Al-Khobar, Saudi Arabia, 811 April 2012.
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Abstract
Foam is a proven method for decreasing gas mobility in both homogeneous and heterogeneous reservoirs. A new foam system,
called multi-phase foam system composed of gas, liquid, and particles has been studied in China recently since it has better
performance than general gas-liquid foam system in profile control.
The aqueous foams prepared by mixtures of pre-performed particles and surfactants were studied in detail. In this article a new
method focusing on liquid drainage velocity was used to estimate the stability of multi-phase foam system compared with
classical foam stability studies that record foam height variation versus time. A synergistic effect on foam stability occurs and
becomes more obvious with increasing surfactant concentration. The synergistic effect mainly comes from the adsorption of
particles on the bubble surface and the formation of a three-dimensional network in the coherent phase. In addition, particle
size is a significant factor affecting foam formation and stability. Foam prepared by 3 different size particles indicates that
foam formability and stability decrease with increasing of particle size. It is hypothesized that the decrease in the foam
formation and stability is related to the particle gravity. Finally, experiments about reservoir conditions like high temperature
and salinity were also conducted. It shows that increasing temperature will accelerate the velocity of foam decay and the
increase of calcium chloride concentration help to stabilize foam while sodium chloride has an optimum concentration for
foam stability.
Introduction
Foam is dispersed in a liquid - gas multiphase dispersion system. With the increased application of foam, an extensive
research has been conducted in recent years (Bernard and Holm(1964), Bertin etal(1998),Donald etal(1988),Hanssen
etal(1994),Kular etal(1989),Nguyen etal(2000),Shan etal(2002)). In order to overcome its decreased performance in profile
control to enhance oil recovery in extremely heterogeneous reservoirs, a novel foam system called multi-phase foam system
has been developed by adding particles into the general gas-liquid foam system, aiming at improving foam stability and
plugging ability. Multi-phase foam system refers to a complex system which contains a great amount of gas-liquid-solid
interfaces and particles are absorbed on bubble surfaces which are formed by stirring intensively the foaming agent solution
containing particles (Kruglyakov etal(2011),Regine and Hans (2002)). This type of foam system has been studied for its
application in EOR in China (Li Binfei etal(2010)) and fire protection in mine. However, there is not much discussion about
the stabilization research of multi-phase foam system for its different formation mechanism and the existence of complex
interfaces.
In this work, a new method to evaluate foam stability has been introduced. And the difference between multi-phase foam
system and general gas-liquid foam system has been analyzed by that approach. In addition, the effects of temperature and
particle size on foam stability were also been investigated and its stabilization mechanism. Furthermore, the stabilization
mechanisms of the multi-phase foam are explored.
Evaluation Method of Foam Stability
At present, the evaluation indexes of foam stability are foaming volume and half life period. However, these two
parameters can not reflect the influence of solid particles on foam performance. Because when the solid particles are added
into the foam, the multi-phase foam formation mechanism is changed. For Warring Blender method, when particle/surfactant
aqueous dispersions are stirred at high rotate speed, it generates a hydrated layer between foam and solid particles. Because of
aqueous dispersion movement and gravitation on the surface, solid particles and foam have a chance to collide each other. The

SPE 160840

schematic drawing of their collision process is shown in the Figure 1(a). After that, solid particles get close to the foam
hydrated layer. Because solid particles get close to the foam, the water between the solid particles and foam is pushed out.
Eventually, the hydrated layer on solid particles surface collide with the hydrated layer on the foam surface. It is shown in the
Figure 1(b). With the additional energy, the hydrated layer becomes thinner and forms hydrated film, the hydrated film shows
instability. Then solid particles get more close to the foam, free energy decreases, the thickness of hydrated film becomes
thinner spontaneously, also solid particles get close to foam spontaneously, it is shown in the Figure 1(c). Finally, hydrated
layer get thinner and then rupture, solid particles absorb onto foam film and form solid-liquid-gas three-phase foam (Figure
1(d)).
The evaluation method of foam stability is mainly Bikerman method. On the base of Bikerman method, Edinzo Iglesias
(Edinzo etal(1995)) figured out that foam height of foaming agent is linear relationship with the logarithm of foam rupture
time in a constant foaming agent concentration. However, this method is based on the Ross-Miles methods. The disadvantage
of the methods is that the test time of foam height is too long. In this paper, foam is generated by Waring Blender method.
When foam is formed, it is put into a measuring cylinder immediately. Then foaming volume (initial foam volume) is
recorded, at the same time the initial time is also recorded. When liquild is drained out 10ml, 20ml, 30ml, 40ml, 50ml from
foam in cylinder, record corresponding time respectively. By analyzing experimental data, foam drainage time is linear
relationship with the foam drainage volume. Slope reflects the influence of solid particles on foam system.

Fig.1 Formation process of multi-phase foam system

The definition of dimensionless foam drainage time t '

t'=

t
t

1/2

(1)

1/ 2

t foam drainage time, min; t half-life period, min; t ' dimensionless foam drainage time, decimals.
In coordinate system, there is a linear relationship between the logarithm of dimensionless time and the reciprocal of the
drainage water volume.

1
log(t ') = a log( ) + b
v

(2)
In this expression, a is foam decay rate and its value is negative. It represents the rate of foam decay. Different foam
system has different foam drainage rate, so the influence of solid particles on the foam stability can be determined.
Experiments
Materials and Apparatus
Materials: Foaming agent HY-2 and SDS are anionic surfactant, CTAB is cationic surfactant. Solid particles consist of
bentonite (NT), micro-fine cement (WN), Pre-performed particle (THL).
Apparatus: Warring Blender agitator, magnetic stirring apparatus, laser particle size analyzer.
Experimental Procedures
(1) Preparation of particle/surfactant aqueous dispersions
At room temperature, use deionized water to prepare foaming agent solution with a certain mass concentration; then mix
the foaming agent solution with different type of solid particles; stir solutions with magnetic apparatus for 12h, until foaming
agents reach adsorption equilibrium on the solid particles surface.
(2) Performance measurement of the foaming system
At room temperature, 100ml aqueous dispersion is stirred with 7000r/min for 3min in Warring Blender agitator; then put
the foam into 500ml measuring cylinder. Record initial time and initial foam volume, and the corresponding time when
solution is drained out 10ml, 20ml, 30ml, 40ml and 50ml, respectively, the period for draining out 50ml solution is half life
period.
(3) Grain size measurement of solid particles
At first, dissolve pre-performed particle (Baojun etal(2007)) into water; then put its disperse system into sample cell.

SPE 160840

Preheat laser particle size analyzer for 30min; and put the sample cell into it; set the parameters, then measure grain size of
solid particles and its regularity of distribution and analyze grain size data statistically.
(4) Observation of multi-phase foam microstructure
When foam is formed by Warring Blender method, put the foam on the glass slide immediately; then get the multi-phase
foam micro-photograph by microscope.
Results
Study on Stability of Two Phase Foam System
Fig.2 Fig.4 shows the three foaming agent foaming volume and half life period in different concentrations. The foaming
volume of CTAB and SDS change very little with the increased foaming agent concentrations, while the foaming volume of
HY-2 would first increase and then reduce. But the stability of HY-2 is much better than the other foaming agents.
Fig.5 Fig.7 represents the effect of foaming agent concentration on foam decay rate. As can be seen in these figures,
liquid volumes which drained from foam are linear with the dimensionless time at constant foaming agent concentrations. The
smaller the slope, the more stable the foam system. And the slope varies at different foaming agent concentrations, that is,
foam decay rate is different which indicate that foam decay rate is related with foaming agent concentrations. The slopes can
be calculated by fitting these experiment data linearly, as seen in Table 1. In Table 1, when the foaming agents are at the same
concentration, the foam decay rate of HY-2 is the smallest, which shows that foam prepared by HY-2 is the most stable
system. The experiment result conforms to the conclusion from the classical method.

Fig.2 Foam ability and foam stability of HY-2 solutions

Fig.3 Foam ability and foam stability of SDS solutions

Fig.4 Foam ability and foam stability of CTAB solutions

Fig.5 The effect of HY-2 concentration on foam decay

rate

Table 1 Foam Decay Rate of Foaming Agents with Different Concentrations

Foaming agents

0.1%

0.3%

0.5%

0.8%

HY-2
CTAB
SDS

/
-0.67497
-0.72001

-0.76503
-0.63515
-0.49564

-0.81991
-0.56951
-0.54233

-0.89303
-0.56755
-0.50421

SPE 160840

Fig.6 The effect of SDS concentration on foam decay rate

Fig.7 The effect of CTAB concentration on foam decay

rate

Effect of Particle types on Stability of Multi-phase Foam System

Foaming ability of multi-phase foam system, which is composed of pre-preformed particles, bentonites, and micro-fine
cements, respectively, has been studied experimentally. The concentration of foaming agent is 0.5% constantly, and the
concentrations of 3 types of solid particles are 0.4%. The experiment results are listed in Table 2. When preparing the multiphase foam solutions, on the one hand, the foaming agents adsorb on the particle surface, which can change the physical and
chemical properties of particle surfaces from hydrophobia to hydrophilic, on the other hand, foaming agents can reduce surface
tension of foaming dispersion effectively, which is favorable to form uniform fine bubbles and increase its stability. While the
foaming volume of multi-phase system will decrease for the addition of particles, and the stability of multi-phase system
composed of bentonites and fine cements would also reduce except pre-performed particles. Therefore, in this work, we
choose pre-preformed particles as the solid phase.
Table 2 Effect of Solid Particles on Foam Ability and Stability of Multi-phase Foam System
Foam synergistic
Particles
Foaming volume/mL
Half life period/min
value/mlmin
375
10.23
3836.25
Pre-performed
350
11.78
4123
particles/THL
Bentonite/NT
370
7.03
2601.1
Fine cements/SN
345
7.12
2456.4
Effect of Solid Particles Size on Multi-Phase Foam Properties
Solid particles absorb onto the surface of the bubble, so its size has a great influence on foam formation and its stability.
It is difficult to adhere to the film if particles are too big. Even if it is adhered, its gravity exceed the capacity of the bubble
anti-deformation, causing the bubble burst. Therefore, the size of the solid particles must meet certain conditions. In our
experiments, three different size of preformed particles (THL-1,THL-2,THL-3) were obtained and then use laser particle size
analyzer to measure their size distribution. Finally, the multi-phase foam was generated by Warring Blender method with three
preformed particles (THL-1,THL-2,THL-3) with the mass concentration of 0.7% and foaming agent(HY-2) of 0.8%.
Table 3 is the statistical data of particle size for THL-1, THL-2 and THL-3. Figure 8 shows the size distribution of three
different preformed particles, containing the cumulative particle size curve and the probability distribution curve. Figure 9
presents the influence of different particle size on foam decay rate. As can be seen from the figure, the variations of the three
curves are basically the same. The slope in the early stage of foam liquid drainage (10-30ml) is greater than the late (30-50ml)
which illustrates the late stage is more stable. This is clearly different from the conventional gas-liquid two-phase foam
system, because the latter foam drainage rate is constant. At the beginning of multi-phase foam generation, a dynamic
equilibrium between the solid particles and foam dont exit. In the early stage, there is collision between particles and bubbles
resulting in foam disappear. After a period of time, the foam system is getting stable, lower decay rate with the particles
distribute at the plateau border. Figure 10 shows the comparison of decay rate between multi-phase foam system and foam
system. From the figures, the stability of foam system is better in the early, but contrary in the late. In summary, we believe
that the solid particles hinder the foams merge, slow down liquid film thinning occurred mainly in the late. Figure 11 shows
the influence of particle size on the foaming ability and half-life period of multi-phase foam system., foaming volume and
half-life period of HY-2 at the mass concentration to 0.8% is respectively 370ml and 14min, when particle THL-1 was added,
the foaming volume reduced to 350ml, while the half-life increased to 18min, and other bigger particles will reduce the
foaming volume and half life period.

SPE 160840

Solid Particles
THL-1
THL-2
THL-3

d 90 ( m )
28.784
36.944
145.366

Table 3 Particle Size Data

d 50 ( m )

d10 ( m)

d av ( m)

18.343
25.110
36.010

9.263
13.749
22.946

18.927
25.491
57.432

(a)

(b)

(c)
Fig.8 Preformed particle size curves (red: size accumulation curve blue: distribution curve)

SPE 160840

Fig.9 Effect of particle size on foam decay rate

Fig.10 Foam decay rate comparison of HY-2 and HY2/THL

Fig.11 Foam ability and stability of multi-phase foam

system with various size particles

Fig.12 Foam ability and foam stability of multi-phase foam

system

Effect of Solid Particles Concentration on Multi-Phase Foam Properties

Fix the foaming agent mass concentration at 0.8%, set the preformed particles mass concentration as 0.4%,0.7%,1% and
1.5% ,respectively. The foaming ability and stability of aqueous dispersion are shown in Figure 12. It shows that with the
increase of solid particles concentration, the foaming ability of the system decreased. Its foam ability is less than a single
foaming agent solution. On the one hand, this is because the surfaces of preformed gel particles are hydrophilic, the foaming
agents would absorb on the surfaces and change their physical and chemical properties. In order to make solid particle surface
hydrophobic, the amount of actual foaming agent for foaming is reduced. On the other hand, the surface activity of the
aqueous dispersion is limited because of the decreased small mass fraction of foaming agent .Figure 13 shows that the
variation of the foam decay rate curves are basically the same as those in Figure 9 with different concentration of THL/HY-2
dispersed system, which illustrate the same mechanism in THL/HY-2 system.
Effect of Temperature and Salinity
As is shown in the Figure 14, in the initial period of foam drainage, NaCl has little influence on the foam drainage rate of
foam system. The slope of the curve is almost the same. However, foam drainage rate varies with NaCl concentration in the
later stage. Especially, the foam drainage rate is the smallest at 3% NaCl concentration and the foam is the most stability.
Another conclusion is that, when the foam drainage volume is the same, the stability of multi-phase foam system is not
proportional to NaCl concentration. There is the most stability value for the foam system.
In general, Ca2+ has a great influence on the foaming agent performance. The influence is different for different foaming
agents. Some foaming agents even cannot generate foams because of the affect by Ca2+. In Figure 15, foam drainage rate
increases with the CaCl2 concentration increased. It is clear that foam system is stability.
With temperature increased, foams swell. Since when temperature rises, molecule thermal motion aggravates,
intermolecular attraction weakens. Actually, when foaming volume reaches peak value, foaming volume decreases with
temperature increased, because water in the foams evaporates due to high temperature.

SPE 160840

Three-phase foam stability reduces with temperature increased. In the initial stage, solid particles considerably raise the
foam thermal resistance at low temperature. Temperature has little influence on the foam drainage and gas diffusion. When
temperature is high, the thermal resistance of solid particles drops rapidly, and protective capability of solid particles and foam
framework weakens.

Fig.13 Effect of particle concentration of multi-phase

foam system

Fig.14 Foam drainage rate affected by NaCl

Fig.15 Foam drainage rate affected by CaCl2

Fig.16 Multi-phase foam system foaming performance

and half life period varies with temperature

Fig.17 Foam drainage rate affected by temperature

Microscopic Images on Multi-Phase Foam System
The foam was immediately put under the microscope to observe, generated by Warring Blender method. The results are
shown in Figure 18. Shuiyan Zhang(Shuiyan etal(2008)) pointed out that the distribution of solid particles in the liquid film
between the foam surface and foam. Due to the foam drainage, the particles will gradually gather in the plateau border. It can
be seen in Figure 18, the foam distribute more evenly and finely in foaming agent solution. Because only the foaming agent

SPE 160840

adsorbed on the surface of the foam, so the strength of the liquid film between the foam is relatively weak and prone to foam
merger. But for Multi-Phase Foam system, when the solid particle concentration is 2%, the particles will adsorb on the film,
and interlock the adjacent foam, as shown in Figure 18(b). The particles at the film can increase the combined resistance
between foams, thereby increasing the foam stability. The thickness of the foam in Figure 18(b) is greater than Figure 18(a),
indicating that part of the particles distribute on the surface of foam, and strengthen thickness of foam surface. These two
factors, particles adsobed on foam surface and liquid film between foams, prevnet foam merger.

(a)
(b)
Fig.18 Optical microscope images of multi-phase foam system
Conclusions
(1)Decay rate difference exits between the multi-phase foam and general gas-liquid foam system because of the solid
particles. The foam decay rate is constant in foam system at constant foaming agent concentration, but for multi-phase foam
system, the decay rate increase first and then decrease.
(2)Solid particles will affect the performance of multi-phase foam system, the smaller the particle size the more stable
multi-phase foam system, the foaming ability and volume would decreased with the increasing particle concentration.
(3)When the foam drainage volume is the same, the stability of multi-phase foam system is not proportional to NaCl
concentration. There is the most stability value for the foam system.
Acknowledgements
This work was financially supported by the National Science and Technology Major Project under Contract NO.
2011ZX05009.We thank Foam Fluid research center of China University of Petroleum for helping with the experimental
design and set-up.
Nomenclature

t'=
t=

dimensionless foam drainage time

foam drainage time, min

t 1/ 2 =

half-life period, min

a=

foam decay rate, cm /min

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SPE 160840

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